Solution-processed perovskite films are rich in surface defects and grain boundaries, which limits their performance and stability in photovoltaic application. Surface passivation using bulky organic cations can effectively reduce the surface defects of a perovskite film without affecting its fundamental properties. Herein, the use of hydrophobic bulky aromatic molecules, namely 4-trifluoromethyl-benzylammonium iodide/bromide (CF₃BZA-I/Br), as defect-passivators to heal the surface defects and grain boundaries of perovskite films is introduced. Owing to the presence of the trifluoromethyl (CF₃) moieties, CF₃BZA-I/Br-passivated perovskite films exhibit a hydrophobic surface with significantly fewer grain boundaries. By suppressing the surface and interfacial imperfections, CF₃BZA-Br-treated perovskite solar cells achieve an outstanding power conversion efficiency (PCE) of 20.75%. The PCE improvement originates mainly from the reduction of trap states and nonradiative carrier recombination. The ultrathin hydrophobic barrier layer formed after passivation also shields the perovskite film surface from moisture ingress and environmental degradation, leading to improved stability of the devices. By optimizing the passivation conditions, the bulky CF₃BZA-I/Br molecules could be the ideal defect passivators, with versatile applications in a wide variety of perovskite optoelectronics.

https://onlinelibrary.wiley.com/doi/abs/10.1002/solr.202100712